CN102723381B - Conductor connection member - Google Patents
Conductor connection member Download PDFInfo
- Publication number
- CN102723381B CN102723381B CN201210211275.0A CN201210211275A CN102723381B CN 102723381 B CN102723381 B CN 102723381B CN 201210211275 A CN201210211275 A CN 201210211275A CN 102723381 B CN102723381 B CN 102723381B
- Authority
- CN
- China
- Prior art keywords
- bond layer
- alligatoring face
- epoxy resin
- micron
- face
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004020 conductor Substances 0.000 title claims abstract description 219
- 229910052751 metal Inorganic materials 0.000 claims abstract description 187
- 239000002184 metal Substances 0.000 claims abstract description 187
- 239000002245 particle Substances 0.000 claims description 147
- 239000003822 epoxy resin Substances 0.000 claims description 79
- 229920000647 polyepoxide Polymers 0.000 claims description 79
- 239000003795 chemical substances by application Substances 0.000 claims description 74
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 43
- 238000009826 distribution Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229920003986 novolac Polymers 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000010931 gold Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- -1 glycidyl ester Chemical class 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000001186 cumulative effect Effects 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 150000002460 imidazoles Chemical class 0.000 claims description 6
- 239000011133 lead Substances 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 238000012644 addition polymerization Methods 0.000 claims description 5
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
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- 239000004925 Acrylic resin Substances 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
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- HHEFNVCDPLQQTP-UHFFFAOYSA-N ammonium perchlorate Chemical compound [NH4+].[O-]Cl(=O)(=O)=O HHEFNVCDPLQQTP-UHFFFAOYSA-N 0.000 description 1
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- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
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- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
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- 238000003475 lamination Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
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- 229920006295 polythiol Chemical class 0.000 description 1
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- 125000006850 spacer group Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
- H01L31/02245—Electrode arrangements specially adapted for back-contact solar cells for metallisation wrap-through [MWT] type solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/28—Metal sheet
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
- H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
- H01L31/0512—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module made of a particular material or composition of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention provides a kind of conductor connection member, it possesses: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming.
Description
The present invention is application number be 200880014826.6(international application no is PCT/JP2008/058486), the divisional application that the applying date is on May 7th, 2008, denomination of invention is the patent application of " conductor connection member, syndeton and solar module ".
Technical field
The present invention relates to conductor connection member, syndeton and solar module.
Background technology
Solar module has following structure: multiple solar battery cell is connected by the distribution component that is electrically connected with its surface electrode and/or is connected in parallel.The connection of electrode and distribution component used solder (for example, referring to patent documentation 1) in the past.Solder is due to excellent on the connection reliability such as conduction and adhesion strength, cheap and have versatility, is therefore widely used.
And on the other hand, from the angle of protection of the environment, studying the distribution method of attachment not using solder.Such as, in following patent documentation 2 and 3, disclose the method for attachment using pasty state or film-form conductive adhesive.
Patent documentation 1: Japanese Unexamined Patent Publication 2004-204256 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2000-286436 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2005-101519 publication
Summary of the invention
The problem to be solved in the present invention
But, in the method for attachment of the solder using patent documentation 1 to record, because the melt temperature of solder is generally about 230 ~ 260 DEG C, therefore the volume contraction connecting adjoint high temperature or solder brings harmful effect to the semiconductor structure of solar battery cell, the characteristic degradation of the solar module manufactured by easily producing.And then, due to the slimming of nearest semiconductor substrate, more easily there is breaking or warpage of battery unit.In addition, use the connection of solder, owing to being difficult to the distance between control electrode and distribution component, therefore, be difficult to dimensional accuracy when fully obtaining assembling.If can not get sufficient dimensional accuracy, the decline of finished product rate can be caused when assembling procedure.
On the other hand, the conductive adhesive recorded as patent documentation 2 and 3 is used to carry out the method for attachment of electrode and distribution component, compared with using the situation of solder, bonding due to what can carry out under low temperature, therefore think the harmful effect to solar cell that high-temperature heating can be suppressed to cause.But, when making solar module by the method, need to repeat following operation to all electrodes: first, the conductive adhesive of coating or lamination pasty state or film-form on the electrode of solar battery cell, thus formation bond layer, then, after the adhesive layer of distribution component and formation is carried out aligned in position, carry out bonding.Therefore, have connection operation miscellaneous, solar module productivity ratio reduces such problem.In addition, the method described in patent documentation 2 and 3, does not consider the impact of the surface state of bonded object, has the situation that can not get abundant connection reliability (connection reliability especially under hot and humid).
The present invention completes based on above-mentioned situation, its object is to provide a kind of conductor connection member, and its connection operation that not only can realize when being electrically connected to each other by electric conductor disconnected from each other simplifies, and can obtain excellent connection reliability.In addition, the object of the present invention is to provide a kind of syndeton and the solar module that can take into account excellent productivity and high connecting reliability.
The method of dealing with problems
In order to solve the problem, the invention provides a kind of conductor connection member, it possesses the metal forming having alligatoring face at least one side of interarea and the bond layer formed on the alligatoring face of this metal forming.
Utilize conductor connection member of the present invention, a part for conductor connection member is configured in the mode that alligatoring face is relative with the electric conductor that should connect, in an opposite direction to its heating pressurization, therewith in the same manner, heating pressurization is carried out to the other parts of conductor connection member and other electric conductor, thus can be electrically connected and bonded metal paper tinsel and each electric conductor, the connection operation that can realize when being electrically connected to each other by electric conductor disconnected from each other simplifies, meanwhile, obtain excellent connection reliability and become possibility.
The present inventor etc. think that the reason obtaining above-mentioned effect is as follows: have said structure by conductor connection member of the present invention, can electric conductor and have the distribution component as each electric conductor of electrical connection effect metal forming between easily arrange and control the bond layer of thickness, well bonding becomes possibility, compared with using the situation of solder, (particularly less than 200 DEG C) electric conductor and metal forming can be connected at lower temperatures, can the breaking or warpage of base material of abundant restraint measure electric conductor, and the conducting of electric conductor and metal forming becomes easy acquisition due to the projection in metal forming alligatoring face, thus the impact of the surface state of electric conductor is lowered.
With regard to electric conductor link of the present invention, from the view point of the conductivity improving electric conductor and metal forming, the maximum height in the above-mentioned alligatoring face being formed with bond layer is set to Ry(μm) time, the thickness t(μm of bond layer) be preferably less than 3 times of Ry.
In this specification, maximum height is the value derived according to the benchmark of JIS-B0601-1994, by by ultra-deep measuring shape microscope (such as, KEYENCES society system, ultra-deep measuring shape microscope " VK-8510 " etc.) observe, and calculated by image measurement analysis software and derive.In addition, the thickness of bond layer is the value measured by miniature measuring instrument.
In addition, in electric conductor link of the present invention, bond layer is preferably containing latent curing agent.
And then in electric conductor link of the present invention, bond layer is preferably containing conducting particles.
In addition, above-mentioned bond layer contains conducting particles, and the maximum height in the above-mentioned alligatoring face being formed with bond layer is set to Ry(μm) time, the average grain diameter D(μm of conducting particles) be preferably below Ry.In this case, contact when can increase connection is counted and can obtain low resistance effect, by preventing being mixed into of bubble in connecting portion, can improve connection reliability further.
In addition, when above-mentioned bond layer contains conducting particles, 10 mean roughness being formed with the above-mentioned alligatoring face of bond layer are set to Rza(μm), 10 mean roughness in the face connected with bond layer of the electric conductor be connected are set to Rzb(μm) time, the maximum particle diameter r of conducting particles
max(μm) be preferably Rza and Rzb with following.By setting the maximum particle diameter of conducting particles as described above according to the surface roughness of electric conductor that should connect and the surface roughness of metal forming, thus, although use the conducting particles with wider domain size distribution, but sufficient cementability and excellent conductivity can be obtained, with use be used for the conducting particles of the uniform particle size of this kind of purposes situation compared with, the raising of connection reliability can be realized with more low cost.
In this specification, 10 mean roughness refer to the value derived according to the benchmark of JIS-B0601-1994, by by ultra-deep measuring shape microscope (such as, KEYENCES society system, ultra-deep measuring shape microscope " VK-8510 " etc.) observe, and calculated by image measurement analysis software and derive.
In addition, with regard to electric conductor link of the present invention, from the view point of obtaining higher levels of connection reliability, above-mentioned bond layer contains latent curing agent and conducting particles, the maximum height being formed with the alligatoring face of bond layer is set to Ry(μm) time, the average grain diameter D(μm of conducting particles) be below Ry, and 10 mean roughness being formed with the alligatoring face of bond layer are set to Rza(μm), 10 mean roughness in the face connected with bond layer of the electric conductor be connected are set to Rzb(μm) time, the maximum particle diameter r of conducting particles
max(μm) be preferably Rza and Rzb with following.
In addition, when above-mentioned bond layer contains latent curing agent, the maximum height in the above-mentioned alligatoring face being formed with bond layer is set to Ry(μm) time, the average grain diameter Dc(μm of latent curing agent) be preferably below Ry.Be below the maximum height in alligatoring face by making the average grain diameter of latent curing agent, when can suppress to apply pressure to the conductor connection member in keeping, the reduction of latent curing agent function, can realize improving cementability while the storage stability fully guaranteeing conductor connection member.For being made by conductor connection member under tape roll folds body situation, above-mentioned condition guarantees that storage stability is effective especially.
By conductor connection member of the present invention, preferred above-mentioned metal forming is banded.In this case, easily form the one fixed width meeting connecting portion, and automation when making it the connection connected in the longitudinal direction becomes easy etc., can obtain the effective effect of simplification to connection operation.
In addition, with regard to conductor connection member of the present invention, from conductivity or the viewpoint such as corrosion resistance, pliability, metal forming is preferably containing more than the a kind metal selected from Cu, Ag, Au, Fe, Ni, Pb, Zn, Co, Ti, Mg, Sn and Al.
In addition, with regard to conductor connection member of the present invention, from the formation easiness of bond layer, the viewpoint such as roughness retentivity adding man-hour, 10 mean roughness Rza(μm in above-mentioned alligatoring face) be preferably less than 30 μm.
The invention provides a kind of syndeton, it is by configuring conductor connection member of the present invention and electric conductor according to the mode making the alligatoring face of conductor connection member relative across described bond layer with described electric conductor and obtaining their heating pressurizations, the electrical connection of this syndeton and bonded metal paper tinsel and electric conductor.
According to syndeton of the present invention, by conductor connection member of the present invention, electric conductor is electrically connected the metal forming as distribution component, thus can simplifies connection operation, and excellent connection reliability can be obtained.If such syndeton of the present invention be applied in the electrical and electronic parts (particularly solar module) needing distribution to connect, then can realize the raising of the productive raising of parts and connection reliability.
With regard to syndeton of the present invention, the mask be connected with metal forming of electric conductor has surface roughness, the protuberance contacts in the projection of the surface roughenings of preferred electric conductor and the alligatoring face of metal forming.
In addition, the invention provides a kind of solar module, it is possess multiple solar module with the solar battery cell of surface electrode, solar battery cell is each other by with adhering part, the metal forming be bonded on described surface electrode is electrically connected, the face connected with surface electrode of metal forming is alligatoring face, and metal forming is arranged by the conductor connection member of the invention described above.
According to solar module of the present invention, by solar battery cell being connected to each other via the metal forming arranged with conductor connection member of the present invention, make easy to manufacture, and excellent connection reliability can be obtained.Therefore, according to solar cell of the present invention, excellent productivity and high connecting reliability can be taken into account.
In solar module of the present invention, preferably by part or all beyond the face connected with surface electrode of resin-coated metal paper tinsel.In this case, the electrical short (short) caused with contacting of other conductive component by metal forming effectively can be prevented, and, due to the corrosion of metal forming can be prevented, the durability of metal forming thus can be improved.
In addition, solar module of the present invention be the conductor connection member being namely provided with bond layer by above-mentioned conductor connection member on the two alligatoring faces that two interareas have the metal forming in alligatoring face solar battery cell is one another in series the solar module be formed by connecting time, each bond layer can have the function of bonded metal paper tinsel and electrode concurrently, and the function of resin as coated metal paper tinsel, this solar module is high reliability, easily manufactures simultaneously.
The effect of invention
According to the present invention, can provide a kind of conductor connection member, its connection operation that not only can realize when being electrically connected to each other by electric conductor disconnected from each other simplifies, and can obtain excellent connection reliability.In addition, according to the present invention, a kind of syndeton and the solar module that can take into account excellent productivity and high connecting reliability can be provided.
Accompanying drawing explanation
Fig. 1 is the schematic section of the execution mode showing the conductor connection member that the present invention relates to.
Fig. 2 is the schematic section of other execution mode showing the conductor connection member that the present invention relates to.
Fig. 3 is for illustration of the surface roughness of the electrode be connected and the figure of relation between the surface roughness in metal forming alligatoring face and bond layer thickness.
Fig. 4 is for illustration of the surface roughness of the electrode be connected and the figure of relation between the surface roughness in metal forming alligatoring face and bond layer thickness.
Fig. 5 is for illustration of the surface roughness of the electrode be connected and the figure of relation between the surface roughness in metal forming alligatoring face and bond layer thickness.
Fig. 6 is the schematic section of the syndeton that display execution mode relates to.
Fig. 7 is the schematic diagram of the solar module important part that display execution mode relates to.
Fig. 8 is the schematic diagram of the solar module part that display execution mode relates to.
Embodiment
Below, as required with reference to accompanying drawing, describe the preferred embodiment of the present invention in detail.In addition, in accompanying drawing, same key element gives prosign, omits repeat specification.Wait position relationship when there is no particular limitation up and down, for based on position relationship shown in accompanying drawing.Further, the dimension scale of accompanying drawing is not limited to illustrated ratio.
Fig. 1 is the schematic section of the execution mode showing the conductor connection member that the present invention relates to.Conductor connection member 10 shown in Fig. 1 possesses the belt metal foil 1 and the 1st bond layer 2 be arranged on metal forming two alligatoring face and the 2nd bond layer 3 that two interareas are alligatoring face 1a, 1b, has the form of the metal forming adhesive tape of band bonding agent.In addition, Fig. 2 is the schematic section of other execution mode showing the conductor connection member that the present invention relates to.Conductor connection member 20 tool shown in Fig. 2 is the belt metal foil 1 of alligatoring face 1a and the 1st bond layer 2 that is arranged on metal forming alligatoring face by the one side of interarea.In addition, the bond layer 2 of conductor connection member 20 is containing latent curing agent 4 and conducting particles 5.
The two sides of metal forming is provided with the conductor connection member 10 of bond layer, during the solar module stated after manufacturing, the connection operation of the surface electrode that easily can carry out connection solar battery cell and the surface electrode (backplate) being arranged on the adjacent solar battery cell back side.That is, owing to being provided with bond layer on two sides, therefore conductor connection member need not be overturn, just can connecting surface electrode and backplate.In addition, do not participate in the bond layer with Electrode connection, by playing the function as the coated material of metal forming, effectively can prevent the electrical short (short) caused with contacting of other conductive component by metal forming, in addition, due to the corrosion of metal forming can be prevented, the durability of metal forming thus can be improved.Even if by conductor connection member 10 for situation about connecting each other the electric conductor be arranged on the same face, also such effect can be obtained.
On the other hand, be just provided with the conductor connection member 20 of bond layer at the one side of metal forming, parts easily make, and are excellent in cost, are suitable for the situation etc. connected each other the electric conductor be arranged on the same face.
Conductor connection member 10,20 has the form of the metal forming adhesive tape of band bonding agent, when folding as tape roll, preferably the barrier films such as processing release paper are set on the face of bond layer, or, when conductor connection member 20, the back side process oxidant layer such as silicon are preferably set at the back side of metal forming 1.
As metal forming 1, such as, can enumerate the metal forming containing more than the a kind metal selected from Cu, Ag, Au, Fe, Ni, Pb, Zn, Co, Ti, Mg, Sn and Al, and the metal forming that they are laminated.In present embodiment, the excellent electric conductivity of Copper Foil and aluminium foil, thus preferably.
The alligatoring face of metal forming 1 can be arranged by such as adopting the known method for coarsening surface such as chemical method such as the physical method of grounds travel or roller etc., etching.
The thickness of metal forming 1 can be about 5 ~ 150 μm.When rolling up folded using the conductor connection member of present embodiment as adhesive tape, from the angle of morphotropism and operability, the thickness of preferable alloy paper tinsel is about 20 ~ 100 μm.In addition, the thickness of metal forming is thin, during undercapacity, can be strengthened by plastic film etc.
As the metal forming used in present embodiment, be provided with the material being commonly referred to as electrolysis paper tinsel of irregular micro concavo-convex in electrochemistry and easily buy, because of but suitable.Particularly as the electrolytic copper foil used in the copper plating film laminated board of printed wiring plate material, easily buying as versatile material, is also suitable economically.It is average 10 ~ 500 μm that this electrolytic copper foil is generally jut base area
2left and right.
To the roughness in alligatoring face, there is no particular limitation, but, if roughness becomes large, have and be difficult to form bond layer, add the tendency being difficult to man-hour fully keep roughness, if roughness is too small, owing to being difficult to obtain sufficient conductivity, therefore maximum height Ry is preferably 3 μm ~ 35 μm.In addition, from the view point of the formation easiness of bond layer or the roughness retentivity adding man-hour, the maximum height Ry in alligatoring face is preferably less than 30 μm, is more preferably less than 25 μm.During with the suitable roughness in 10 mean roughness setting alligatoring faces, 10, alligatoring face mean roughness Rza is preferably less than 30 μm, is more preferably less than 25 μm, is particularly preferably less than 15 μm.
As bond layer 2,3, can extensive use containing thermoplastic or by heat or light and show curability curable material formed bond layer.In present embodiment, from the thermal endurance after connection or excellent moisture resistance, bond layer is preferably containing curable material.As curable material, can heat-curing resin be enumerated, known material can be used.As heat-curing resin, such as, can enumerate epoxy resin, phenoxy resin, acrylic resin, phenol resin, melmac, polyurethane resin, mylar, polyimide resin, polyamide etc.Wherein, from the view point of connection reliability, in bond layer, preferably contain at least one in epoxy resin, phenoxy resin and acrylic resin.
In addition, bond layer 2,3 preferably contains the latent curing agent of heat-curing resin and this heat-curing resin.The reaction produced by heat and/or pressure of latent curing agent, active site is relatively clearer and more definite, is suitable for the adjoint method of attachment of heating pressurization.Further, bond layer 2,3 more preferably contains the latent curing agent of epoxy resin and epoxy resin.The bond layer formed by the epoxy bonding agent containing latent curing agent is owing to can solidify the short time, and attended operation is good, excellent in adhesion on molecular structure, therefore particularly preferably.
As above-mentioned epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, bisphenol A novolak epoxy resin, Bisphenol F novolac epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanuric acid ester type epoxy resin, aliphat chain epoxy resin etc. can be enumerated.These epoxy resin can be halogenated, also can hydrogenation.Two or more kinds may be used for these epoxy resin.
As latent curing agent, anionic polymerization catalyst type curing agent, cationically polymerizable catalyst type curing agent and addition polymerization type curing agent etc. can be enumerated.These can be used alone or use as two or more mixture.In these, from having excellent fast curing, do not need to consider that stoichiometric angle is set out, preferred anionic or cationically polymerizable catalyst type curing agent.
Catalyst type curing agent as anion or cationically polymerizable such as can enumerate the salt, dicyandiamide etc. of tertiary amines, imidazoles, hydrazides based compound, boron trifluoride-amine complex, salt (sulfosalt, ammonium salt etc.), Amino carboximides, diaminomaleonitrile, melamine and derivative thereof, polyamine, also can use these modifier.Curing agent as addition polymerization type can enumerate polynary amine, polythiol class, polyhydric phenols and acid anhydrides etc.
When using tertiary amines or imidazoles as anionic polymerization catalyst type curing agent, epoxy resin is cured by the heating carried out under temperature in 160 DEG C ~ about 200 DEG C about several 10 seconds ~ a few hours.Therefore, the up time (storage life) is long, thus preferably.
As cationically polymerizable catalyst type curing agent, make the photonasty salt of epoxy resin cure (mainly using aromatic diazonium salt, aromatic series sulfosalt etc.) preferably by irradiation energy line.Carry out activate as the heating beyond being irradiated by energy line and make the curing agent of epoxy resin cure, having aliphat sulfosalt etc.This curing agent owing to having rapidly-curable, therefore preferably.
Be coated to these curing agent with the polymer substance such as polyurethane series, Polyester or the inorganic matter such as the metallic film such as nickel, copper and calcium silicates and carried out the material of microencapsulation, due to the up time can be extended, therefore preferably.
The active temperature of bond layer is preferably 40 DEG C ~ 200 DEG C, is more preferably 50 DEG C ~ 150 DEG C.If active temperature is less than 40 DEG C, then with the having a narrow range of temperature of room temperature (25 DEG C), the preservation of connection member needs low temperature, and on the other hand, if more than 200 DEG C, easily produces thermal impact to the parts beyond coupling part.In addition, the active temperature of bond layer is using bond layer as sample, uses DSC(differential scanning calorimeter), exothermal peak temperature when heating up from room temperature with 10 DEG C/min.
In addition, with regard to the active temperature of bond layer, if be set in low temperature side, improve although reactive, have the tendency that keeping quality reduces, therefore preferably consider that these decide.That is, by the conductor connection member of present embodiment, can be connected to by the heat treatment below the active temperature of bond layer on the electric conductor that is arranged on substrate temporarily, the substrate being with metal forming and bond layer can be obtained.Then, by being set in above-mentioned scope by the active temperature of bond layer, fully guaranteeing bond layer conservatory while, easily realize connection excellent in reliability when being heated to more than active temperature.Thereby, it is possible to more effectively realize connecting 2 stage solidification to be cured together after product collect etc. temporarily.In addition, when making the interim connection product as above-mentioned, almost do not rise along with the viscosity of the bond layer of curing reaction below active temperature, therefore, excellent to the fillibility of the micro concavo-convex of electrode, can easily be carried out the such effect of manufacturing management.
With regard to the conductor connection member of present embodiment, utilize the roughness in the alligatoring face of metal forming can obtain the conductivity of thickness direction, but the quantity of male and fomale(M&F) when connecting from increase, increase contacts the angle of counting and sets out, and bond layer is preferably containing conducting particles.
As conducting particles, there is no particular limitation, such as, can enumerate gold particle, silver particles, copper particle, nickel particles, gold-plated nickel particle, gold/nickel plated plastic particle, copper facing particle, nickel plating particle etc.In addition, conducting particles, from the view point of conducting particles for when connecting by the concavo-convex imbedibility of sticker surface, preferably there is Mao Lizhuan or spherical shape of particle.That is, the conducting particles of shape like this, even for metal forming or by the complex unevenness on its shape of sticker surface, its imbedibility is also high, the tracing ability for variations such as the vibration after connecting or expansions is high, can improve connection reliability further.
The conducting particles of present embodiment, domain size distribution is about 1 ~ 50 μm, preferably can use the conducting particles of 1 ~ 30 μm of scope.
As long as the content of conducting particles contained in bond layer is just passable in the scope significantly not reducing bond layer cementability, such as, using bond layer cumulative volume as benchmark, can be 10 below volume %, be preferably 0.1 ~ 7 volume %.
In the electric conductor link of present embodiment, when above-mentioned bond layer contains the situation of conducting particles, cementability and conductivity is taken into account from the view point of high-caliber, the maximum height being formed with the alligatoring face of bond layer is set to Ry(μm) time, the average grain diameter D(μm of conducting particles) be preferably below Ry.Thereby, it is possible to the contact increased when connecting is counted thus obtains the effect of low resistance, by preventing from being mixed into bubble in connecting portion, thus connection reliability can be improved further.
In addition, when above-mentioned bond layer contains conducting particles, 10 mean roughness being formed with the alligatoring face of bond layer are set to Rza(μm), 10 mean roughness in the face connected with bond layer of the electric conductor be connected are set to Rzb(μm) time, the maximum particle diameter r of conducting particles
max(μm) is preferably less than or equal to Rza and Rzb sum, the maximum particle diameter r of conducting particles
max(μm) is more preferably and is less than or equal to Rza.The maximum particle diameter of conducting particles is set as described above according to the surface roughness of electric conductor that will connect and the surface roughness of metal forming, thus use has wider domain size distribution (such as, 1 ~ 50 μm, be preferably the scope of 1 ~ 30 μm) conducting particles and sufficient cementability and excellent conductivity can be obtained, compared with being used in this purposes the conducting particles of conventional uniform particle size, the raising of connection reliability can be realized under more low cost.
In addition, in the conductor connection member of present embodiment, from the view point of reaching higher levels of connection reliability, preferred above-mentioned bond layer contains latent curing agent and conducting particles, the maximum height being formed with the alligatoring face of bond layer is set to Ry(μm) time, the average grain diameter D(μm of conducting particles) be below Ry, and 10 mean roughness being formed with the alligatoring face of bond layer are set to Rza(μm), 10 mean roughness in the face connected with bond layer of the electric conductor be connected are set to Rzb(μm) time, the maximum particle diameter r of conducting particles
max(μm) is preferably less than or equal to Rza and Rzb sum.
In addition, in the conductor connection member of present embodiment, when bond layer contains latent curing agent, the maximum height being formed with the alligatoring face of bond layer is set to Ry(μm) time, the average grain diameter Dc(μm of latent curing agent) be preferably below Ry.By the maximum height making the average grain diameter of latent curing agent be less than or equal to alligatoring face, the decline of the latent curing agent function when applying pressure to the conductor connection member in keeping can be suppressed, the raising of cementability can be reached while the storage stability fully guaranteeing conductor connection member.Above-mentioned condition to storage stability conductor connection member is formed as when tape roll folds body guarantee effective especially.
In addition, when bond layer contains latent curing agent and conducting particles, by conservatory raising or more being balanced by the surface of bond layer and can taking into account the angle of cementability and conductivity, preferably the average grain diameter Dc of latent curing agent is less than the average grain diameter D of conducting particles further.In this specification, the average grain diameter D of conducting particles is the value obtained by following formula.The average grain diameter Dc of latent curing agent is also the value obtained that uses the same method.
[mathematical expression 1]
D＝∑nd/∑n
Here, in formula, n represents that maximum particle diameter is the number of the particle of d.As the assay method of particle diameter, normally used electron microscope or light microscope, Ku Erte grain count instrument, light scattering method etc. can be enumerated.In addition, when particle has aspect ratio, d adopts center-diameter.In the present invention, preferably measure with the particle of electron microscope to minimum more than 10.
In present embodiment, bond layer thickness sets aptly using the average distance of the bottom (recess) in distance alligatoring face as benchmark, but from the viewpoint of cementability, preferably more thick better, from the viewpoint of conductivity, preferably get over Bao Yuehao.If consider this two kinds of characteristics, then the thickness of bond layer is preferably 5 ~ 50 μm, from the viewpoint of improving connection reliability further, is more preferably 9 ~ 45 μm.
In addition, in the conductor connection member of present embodiment, the thickness t(μm of bond layer) preferably set according to the surface state of the electric conductor connected.Below, the surface state of electric conductor is roughly divided into 3 groups, with reference to accompanying drawing, the suitable bond layer thickness in respective situation is described.
Fig. 3 ~ 5 are for illustration of the surface roughness of the electrode be connected and the figure of relation between the surface roughness in metal forming alligatoring face and bond layer thickness.Fig. 3 represent the electric conductor be connected be have almost level and smooth by the situation of the electrode 6a of bonding plane 7a.In addition, Fig. 5 represents that the electric conductor be connected is have the situation by the electrode 6c of bonding plane 7c, by the maximum height Ry equal extent in the roughness of bonding plane 7c and metal forming alligatoring face.In addition, Fig. 4 represents that the electric conductor be connected is have the situation by the electrode 6b of bonding plane 7c, described by the roughness levels of bonding plane 7c shown in Fig. 3 almost level and smooth by shown in bonding plane 7a and Fig. 5 and metal forming alligatoring face maximum height Ry equal extent roughness bonding plane 7c between.
In Fig. 3, the projection in the alligatoring face of metal forming 1 is with when being contacted by bonding plane 7a, preferably by the thickness ta(μm of bond layer) be set as the maximum height Ry(μm with the alligatoring face of metal forming) almost identical, to make to be filled by bonding agent fully between the bottom 8 in the bottom 9a of bonding plane 7a and metal forming 1 alligatoring face.Specifically, the thickness ta of bond layer is preferably as follows setting: as central value, before and after it, arrange Safe width using the value (value of ta/Ry=about 1.0) almost identical with the maximum height (μm) in the face that bond layer connects with electric conductor.Wherein, Safe width such as can be considered following because usually setting: as shape and the roughness of the electrode surface of the electric conductor be connected, the roughness of metal forming and shape, the flow behavior of bond layer, and the amount of exposing etc. of bonding agent when connecting is because usually setting.In present embodiment, be preferably make above-mentioned ta/Ry in the scope of about 0.7 ~ 1.2 by the range set of Safe width.At this moment, easily the concavo-convex of metal forming alligatoring face is used flexibly, therefore preferably.
The situation of Fig. 4, the projection in the alligatoring face of metal forming 1 is with when being contacted by bonding plane 7b, preferably by the thickness tb(μm of bond layer) be set as the maximum height Ry(μm in metal forming alligatoring face) 1 ~ 2 times, with make by between the bottom 8 in the alligatoring face of the bottom 9b of bonding plane 7b and metal forming 1 fully fill by bonding agent.
The situation of Fig. 5, the projection in the alligatoring face of metal forming 1 is with when being contacted by bonding plane 7c, preferably by the thickness tc(μm of bond layer) be set as the maximum height Ry(μm in the alligatoring face of metal forming) 2 ~ 3 times, with make by between the bottom 8 in the alligatoring face of the bottom 9c of bonding plane 7c and metal forming 1 fully fill by bonding agent.
If consider situation as shown in Figure 3 or obtained the impact of electric conductor surface roughness and the mobility etc. of bonding agent such as the situation shown in Fig. 4 and Fig. 5 of conductivity by the contact of non-typical minute asperities, be then Ry(μm in the maximum height in the above-mentioned alligatoring face by being formed with bond layer) time, from the viewpoint of obtaining high connecting reliability, the thickness t(μm of bond layer) be preferably less than 3 times of Ry, be more preferably 0.7 ~ 3 times.The thickness t(μm of bond layer) if more than 3 times of Ry, be then difficult to obtain sufficient conductivity.In addition, the thickness t(μm of bond layer) if less than 0.7 times of Ry, be then difficult to obtain sufficient cementability.
In addition, the present inventor etc. think, as described above with the maximum height in metal forming alligatoring face for benchmark sets the thickness of bond layer thus the reason that easily can obtain high connecting reliability is: the interval of metal forming and electric conductor depends on the difference of height the best part of the concavo-convex roughness of metal foil surface to a great extent, i.e. Ry, therefore, by setting the thickness of bond layer using this Ry as index, even if when electric conductor surface state is uneven, also can more really and easily take into account fillibility and conductivity both sides.
For bond layer 2,3, except mentioned component, curing agent can also be contained, curing accelerator, and it is material modified for silane series coupling agent, the titanate esters system coupling agent or Aluminate system coupling agent etc. improving and be provided with the cementability of base material of electric conductor or wettability, or for dispersants such as the calcium phosphate of the dispersiveness that improves conducting particles or calcium carbonate, for suppressing the chelating material etc. of silver or copper migration etc.
The conductor connection member of present embodiment described above, by being configured on electric conductor, carries out heating pressurization, not only can bonded metal paper tinsel and electric conductor, and can realize the display 10 between metal forming and electric conductor when being energized
-1Ω/cm
2the conducting of the low resistive of following degree.
The conductor connection member of present embodiment is suitable for as the connection member for multiple solar cell is connected each other and/or connected side by side.
Next, the method for attachment of the electric conductor using the conductor connection member of present embodiment is described.
Electric conductor method of attachment of the first embodiment is: use conductor connection member 10 to be electrically connected the 1st electric conductor disconnected from each other and the method for the 2nd electric conductor, comprise following two operations: a part for configuration conductor connection member 10 and the 1st electric conductor, make the alligatoring face 1a of conductor connection member 10 relative across the 1st bond layer 2 with the 1st electric conductor, to their heating pressurizations, metal forming 1 and the 1st electric conductor are electrically connected and by the 1st bonding operation; And, the other parts of configuration conductor connection member 10 and the 2nd electric conductor, make the alligatoring face 1b of conductor connection member 10 relative across the 2nd bond layer 3 with the 2nd electric conductor, to their heating pressurizations, metal forming 1 and the 2nd electric conductor are electrically connected and by the 2nd bonding operation.Thus, the 1st electric conductor and the 2nd electric conductor are electrically connected by the metal forming 1 be bonded on electric conductor.The electric conductor method of attachment of present embodiment is such as suitable for multiple solar battery cell to be connected in series each other.
In addition, above-mentioned 1st operation and the 2nd operation can be carried out simultaneously, also can be undertaken by the order of the 1st operation and the 2nd operation or its contrary order.In addition, above-mentioned 2nd operation also can be other parts and the 2nd electric conductor of configuration conductor connection member 10, make the alligatoring face 1a of conductor connection member 10 relative across the 1st bond layer 2 with the 2nd electric conductor, to their heating pressurizations, metal forming 1 and the 2nd electric conductor are electrically connected and bonding.This situation is suitable for such as by situation etc. that multiple solar battery cell is connected in parallel each other.
Electric conductor method of attachment of the second embodiment is: use conductor connection member 20 to be electrically connected the 1st electric conductor disconnected from each other and the method for the 2nd electric conductor, comprise following two operations: a part for configuration conductor connection member 20 and the 1st electric conductor, make the alligatoring face 1a of conductor connection member 20 relative across the 1st bond layer 2 with the 1st electric conductor, to their heating pressurizations, metal forming 1 and the 1st electric conductor are electrically connected and by the 1st bonding operation; And, the other parts of configuration conductor connection member 20 and the 2nd electric conductor, make the alligatoring face 1a of conductor connection member 20 relative across the 1st bond layer 2 with the 2nd electric conductor, to their heating pressurizations, metal forming 1 and the 2nd electric conductor are electrically connected and by the 2nd bonding operation.Thus, the 1st electric conductor and the 2nd electric conductor are electrically connected by the metal forming 1 be bonded on electric conductor.In addition, above-mentioned 1st operation and the 2nd operation can be carried out simultaneously, also can be undertaken by the order of the 1st operation and the 2nd operation or its contrary order.The electric conductor method of attachment of present embodiment is suitable for such as by situation etc. that multiple solar battery cell is connected in parallel each other.
As the electric conductor in above-mentioned 1st execution mode and electric conductor method of attachment of the second embodiment, such as, can enumerate the semi-conducting electrode or show electrode etc. of the bus electrode of solar battery cell, the shielding distribution of electromagnetic wave shielding or grounding electrode, short-circuit mode purposes.
As the bus electrode of solar battery cell, can enumerate as the known material that can conduct the glass cement usually containing silver or in adhesive resin, be dispersed with the elargol of various conducting particles, gold size, carbon paste, nickel glue, aluminium glue and by burning till or evaporation and the ITO etc. that formed, from the view point of thermal endurance, conductivity, stability and cost, be suitable for the glass cement electrode using argentiferous.In addition, on the semiconductor substrate that the situation of solar battery cell is mainly formed at least one by single crystalline Si, polycrystalline Si, amorphous Si, Ag electrode and Al electrode are set respectively by silk screen printing etc.At this moment the concavo-convex situation that electrode surface has usual 3 ~ 30 μm is had.The electrode particularly formed in solar battery cell, its maximum height Ry is about 30 μm, and 10 mean roughness Rz are about 2 ~ 30 μm, are generally 2 ~ 18 μm, and thick situation is many.
In addition, in 1st execution mode and electric conductor method of attachment of the second embodiment, when above-mentioned bond layer contains conducting particles, from the view point of taking into account cementability and conductivity at a high level, Ry(μm is set in the maximum height in the alligatoring face by being formed with bond layer) time, the average grain diameter D(μm of conducting particles) be preferably below Ry.In addition, when above-mentioned bond layer contains conducting particles, Rza(μm is set at 10 mean roughness in the alligatoring face by being formed with bond layer), 10 mean roughness in the face connected with bond layer of the electric conductor be connected are set to Rzb(μm) time, the maximum particle diameter r of conducting particles
max(μm) is preferably less than or equal to Rza and Rzb sum, the maximum particle diameter r of conducting particles
max(μm) is more preferably below Rza.In addition, will the maximum height in the alligatoring face of bond layer be formed with for establishing Ry(μm) time, from the view point of obtaining high connecting reliability, the thickness t(μm of bond layer) be preferably less than 3 times of Ry, be more preferably 0.7 ~ 3 times.
In the method for attachment of electric conductor of the present embodiment, from the view point of obtaining higher levels of connection reliability, above-mentioned bond layer is preferably containing latent curing agent and conducting particles, Ry(μm is set in the maximum height in the alligatoring face by being formed with bond layer) time, the average grain diameter D(μm of conducting particles) be preferably below Ry, and be set to Rza(μm at 10 mean roughness in the alligatoring face by being formed with bond layer), 10 mean roughness in the face connected with bond layer of the electric conductor be connected are set to Rzb(μm) time, the maximum particle diameter r of conducting particles
max(μm) is preferably less than or equal to Rza and Rzb sum.In addition, when above-mentioned bond layer contains latent curing agent, will the maximum height in the above-mentioned alligatoring face of bond layer be formed with for establishing Ry(μm) time, the average grain diameter Dc(μm of latent curing agent) be preferably below Ry.
As long as the condition of heating-up temperature and moulding pressure can guarantee the electrical contact between metal forming and electric conductor, and electric conductor and metal forming by bond layer by bonding scope, just there is no particular limitation.In addition, all conditions of this pressurization and heating are suitably selected according to the purposes used, each composition in bond layer, the material etc. of base material that arranges electric conductor.Such as, when bond layer is the situation of bond layer containing heat-curing resin, as long as the temperature that solidification occurs heating-up temperature heat-curing resin is just passable.In addition, as long as moulding pressure is between abundant closely sealed electric conductor and metal forming, and the scope not damaging electric conductor or metal forming etc. is just passable.Further, as long as heating does not exceedingly transmit heat to the base material etc. arranging electric conductor pressing time, do not make these material damages or rotten time just passable.Specifically, moulding pressure is preferably 0.1MPa ~ 10MPa, and heating-up temperature is 100 DEG C ~ 220 DEG C, and heating is preferably less than 60 seconds pressing time.In addition, in these conditions, low pressure, low temperature and short time are preferred.
Fig. 6 is the schematic section showing the syndeton that the present invention relates to.Syndeton shown in Fig. 6 30 is by being with the metal forming adhesive tape of bonding agent by the conductivity connection member 20(of present embodiment) a part and the electrode of electric conductor, according to making the alligatoring face of conductor connection member configure across the mode that bond layer is relative with electrode, their heating pressurizations are obtained; It has following structure: the jut of the direct contact electrode 6 of a part of the jut in the alligatoring face of the metal forming 1 of conductivity connection member 20, and metal forming 1 and electrode 6 bonding by the solidfied material 2a of bond layer 2.In addition, in syndeton 30, except the part of the jut in the alligatoring face of metal forming 1 contacts with the jut of electrode 4, the contact point produced by conducting particles 5 also increases.By such syndeton, metal forming 1 and electrode 6 by bonding plane 7 by the bonding force of bonding agent or cure shrinkage power and the maintenance that is fixed, thus the conductivity obtained between metal forming 1 and electrode 6 is stably maintained, electric conductor connection reliability each other can be made sufficient.
The conductor connection member of present embodiment described above is as being suitable for connecting and/or being connected in parallel solar battery cell link each other.Solar cell contains solar module and forms, this solar module is for connecting multiple solar battery cell and/or being connected in parallel, in order to environment resistant and be clipped in tempered glass etc., bury with the resin with the transparency and fill gap, and there is the solar module of outside terminal.
Here, Fig. 7 is the schematic diagram of the solar module important part of display present embodiment, shows the structure sketch map that mutual distribution is connected with multiple solar module.Fig. 7 (a) shows the face side of solar module, and Fig. 7 (b) shows rear side, and Fig. 7 (c) shows side.
As shown in Fig. 7 (a) ~ (c), solar module 100 is, multiple solar battery cell is connected to each other by distribution component 10a, and described solar battery cell is formed with gate electrode 12 and bus electrode (surface electrode) 14a, overleaf side in semiconductor wafer 11 face side and is formed with that backplate 13 and bus electrode (surface electrode) 14b formed.One end of distribution component 10a is connected with the bus electrode 14a as surface electrode, and the other end is connected with the bus electrode 14b as surface electrode.Distribution electrode 10a uses conductivity connection member 10 to arrange.Specifically, the end side of conductivity connection member 10 is configured on bus electrode 14a, make the alligatoring face 1a of conductor connection member 10 relative across the 1st bond layer 2 with bus electrode 14a, in an opposite direction to they heating pressurizations, another side of conductivity connection member 10 is configured on bus electrode 14b, make the alligatoring face 1b of conductor connection member 10 relative across the 2nd bond layer 3 with bus electrode 14b, in an opposite direction to they heating pressurizations, thus be provided with distribution component 10a.
In present embodiment, metal forming 1 and bus electrode 14a and metal forming 1 and bus electrode 14b also can be connected across conducting particles.
In addition, Fig. 8 is the sectional view of the VIII-VIII line along the solar module shown in Fig. 7 (c).Only show the face side of semiconductor wafer 11 in Fig. 8, omit the formation about rear side.The solar module of present embodiment is by be arranged on the end side of conductivity connection member 10 on bus electrode 14a and to carry out heating pressurization operation and make, and it has metal forming 1 and bus electrode 14a and to be electrically connected and by the solidfied material 2a of the bond layer 2 that is filled in bus electrode 14a surface roughenings by bonding structure.Further, in present embodiment, the part beyond the face connected with bus electrode 14a of metal forming 1 is coated to by the solidfied material (preferred resin) of bonding agent.Specifically, the face of the opposition side in the face connected with bus electrode 14a of metal forming 1 is coated to by the solidfied material 3a of the 2nd bond layer 3, and the side of metal forming 1 is coated to by the solidfied material 15 of the bonding agent (residue bonding agent) extruded because heating when connecting is pressurizeed.By such structure, effectively can prevent the electrical short (short) caused by metal forming contacts with other conductive component, and the corrosion of metal forming can be prevented, thus the durability of metal forming can be improved.
In addition, as in the present embodiment, when conductivity connection member 10 is adhesive tape-like, the width of parts is very little compared with length direction, the bonding agent extruded to metal forming side surface direction therefore can be made to increase, the effect of the connecting portion intensity that is easily enhanced.
Above, although the description of suitable execution mode of the present invention, but the present invention is not by the restriction of above-mentioned execution mode.The present invention not departing from the scope of its aim, can carry out various distortion.
Conductor connection member of the present invention is not only applicable to the situation of above-mentioned making solar cell, and is applicable to such as to make the situation such as wiring lead parts of the short-circuit mode such as electromagnetic wave shielding, tantalum capacitor, aluminium electrolytic capacitor, ceramic capacitor, power transistor, various transducer, MEMS associated material, display material.
Embodiment
Below, enumerate embodiment and illustrate the present invention, but the present invention is not limited to the examples.
Embodiment 1
(1) making of the metal forming adhesive tape (conductor connection member) of bonding agent is with
In 175g ethyl acetate, dissolve the phenoxy resin (Inchem society system, trade name " PKHA ", molecular weight be the high molecular expoxy resin of 25000) of 50g as filmogen and the epoxy resin (Nippon Kayaku K. K's system, trade name " EPPN ") of 20g, obtain solution.Then, in above-mentioned solution, add the parent sizing material type curing agent (Asahi Chemical Industry Co., Ltd system, trade name " NOVACURE ", average grain diameter be 2 μm) that in liquid epoxy resin be dispersed with imidazoles system micro-capsule of 5g as latent curing agent, obtain the bond layer formation coating fluid that solid constituent is 30 quality %.In addition, the active temperature of this coating fluid is 120 DEG C.
Then, use roll-coater at the two sided coatings above-mentioned bond layer formation coating fluid of two sides alligatoring electrolytic copper foil (thickness: 35 μm, surface 10 average surface roughness Rza:12 μm, maximum height Ry:13 μm), by it 110 DEG C of dryings 5 minutes, form the bond layer that thickness is 14 μm, obtain duplexer.
Next, above-mentioned duplexer is involved in the polyethylene film as spacer on bond layer, while obtain the winding frizz of tubular.This frizz is cut out as wide 2.0mm, thus obtains the metal forming adhesive tape being with bonding agent.
(2) connection of the solar battery cell of the metal forming adhesive tape of band conductive adhesive is used
Prepare the solar battery cell (thickness: 150 μm, size 15cm × 15cm) being provided with the surface electrode (wide 2mm × long 15cm, 10 average surface roughness Rzb:2 μm, maximum height Ry:13 μm) formed by silver-colored glass cement on the surface of silicon wafer.
Then, aligned in position is carried out by by the metal forming adhesive tape of band bonding agent obtained above and the surface electrode of solar battery cell, use crimping tool (device name AC-S300, daily use chemicals plant engineering society system), 170 DEG C, 2MPa, heating pressurization under the condition of 20 seconds, carry out bonding.Obtain the syndeton being connected with the distribution component formed by electrolytic copper foil on the surface electrode of solar battery cell across conductivity adhesive film like this.
Embodiment 2
Except the Mao Lizhuan Ni powder that the particle diameter distribution width adding 2 volume % in bond layer formation coating fluid is 1 ~ 12 μm (average grain diameter: 7 μm), according to operation similarly to Example 1, obtain the metal forming adhesive tape being with bonding agent.Then, use the metal forming adhesive tape of this band bonding agent, according to operation similarly to Example 1, obtain syndeton.In addition, the conducting particles added did not carry out uniform particle diameter process, has the particle of above-mentioned domain size distribution wide like this.
Embodiment 3
Except using thickness to be that the one side alligatoring Copper Foil (10 average surface roughness Rza:12 μm, the maximum height Ry:13 μm in alligatoring face) of 100 μm is as metal forming, this roughening of copper foil face is provided with beyond bond layer, according to operation similarly to Example 1, obtain the metal forming adhesive tape being with bonding agent.Then, the metal forming adhesive tape of this band bonding agent is alignd with at the enterprising line position of surface electrode, makes alligatoring face relative with surface electrode, according to operation similarly to Example 1, obtain syndeton.
Embodiment 4
Except using thickness to be that the one side alligatoring aluminium foil (10 average surface roughness Rza:12 μm, the maximum height Ry:13 μm in alligatoring face) of 20 μm is as metal forming, this aluminium foil alligatoring face is provided with beyond bond layer, according to operation similarly to Example 1, obtain the metal forming adhesive tape being with bonding agent.Then, by the metal forming adhesive tape of this band bonding agent in the enterprising line position alignment of surface electrode, make alligatoring face relative with surface electrode, according to operation similarly to Example 1, obtain syndeton.
Embodiment 5
Be that the two sides alligatoring electrolytic copper foil (10 average surface roughness Rza:2 μm, the maximum height Ry:3 μm on surface) of 75 μm is as metal forming except using thickness, the thickness of bond layer is made to be beyond 9 μm, according to operation similarly to Example 1, obtain the metal forming adhesive tape being with bonding agent.Then, use the metal forming adhesive tape of this band bonding agent, according to operation similarly to Example 1, obtain syndeton.
Embodiment 6
Be that the two sides alligatoring electrolytic copper foil (10 average surface roughness Rza:9 μm, the maximum height Ry:10 μm on surface) of 75 μm is as metal forming except using thickness, the thickness of bond layer is beyond 18 μm, according to operation similarly to Example 1, obtain the metal forming adhesive tape being with bonding agent.Then, use the metal forming adhesive tape of this band bonding agent, according to operation similarly to Example 1, obtain syndeton.
Embodiment 7
Be that the two sides alligatoring electrolytic copper foil (10 average surface roughness Rza:20 μm, the maximum height Ry:25 μm on surface) of 75 μm is as metal forming except using thickness, the thickness of bond layer is made to be beyond 20 μm, according to operation similarly to Example 1, obtain the metal forming adhesive tape being with bonding agent.Then, use the metal forming adhesive tape of this band bonding agent, according to operation similarly to Example 1, obtain syndeton.
Embodiment 8
Be that the two sides alligatoring electrolytic copper foil (10 average surface roughness Rza:20 μm, the maximum height Ry:25 μm on surface) of 75 μm is as metal forming except using thickness, the thickness of bond layer is made to be 45 μm, the average grain diameter of latent curing agent (capsule footpath) is made to be beyond 4 μm, according to operation similarly to Example 1, obtain the metal forming adhesive tape being with bonding agent.In addition, the active temperature of coating fluid is 115 DEG C.Then, use the metal forming adhesive tape of this band bonding agent, as solar battery cell, use the solar battery cell (thickness: 150 μm, size is 15cm × 15cm) being provided with the surface electrode (wide 2mm × long 15cm, 10 average surface roughness Rzb:18 μm, Ry:20 μm) formed by silver-colored glass cement on the surface of silicon wafer, in addition, according to operation similarly to Example 1, obtain syndeton.
Embodiment 9
Except the particle diameter distribution width adding 2 volume % in the bond layer formation coating fluid of embodiment 8 be 1 ~ 12 μm (average grain diameter: 7 μm, without classification) cover except plastic pellet (being coated to the surface of polystyrene particle with Ni/Au), according to operation similarly to Example 8, obtain the metal forming adhesive tape being with bonding agent.Then, use the metal forming adhesive tape of this band bonding agent, according to operation similarly to Example 8, obtain syndeton.
Reference example 1
Be that the two sides alligatoring electrolytic copper foil (10 average surface roughness Rza:12 μm, the maximum height Ry:13 μm on surface) of 75 μm is as metal forming except using thickness, the thickness of bond layer is made to be beyond 52 μm, according to operation similarly to Example 1, obtain the metal forming adhesive tape being with bonding agent.Then, use the metal forming adhesive tape of this band bonding agent, according to operation similarly to Example 1, obtain syndeton.
Comparative example 1
Except use thickness be the smoothing electrolytic Copper Foil (surface 10 average surface roughness Rza:0.2 μm, maximum height Ry:0.3 μm) of 35 μm as except metal forming, according to operation similarly to Example 1, obtain the metal forming adhesive tape being with bonding agent.Then, use the metal forming adhesive tape of this band bonding agent, according to operation similarly to Example 1, obtain syndeton.
Evaluate
To the syndeton of above-described embodiment 1 ~ 9, reference example 1 and comparative example 1, evaluate deltaF.F. as follows.Result is shown in table 1.
deltaF.F.
Solar simulator (WACOM electricity Chuan society system, trade name " WXS-155S-10 ", AM:1.5G) is used to measure the IV curve of the syndeton obtained.In addition, by syndeton 85 DEG C, leave standstill 1500 hours under the hot and humid atmosphere gas of 85%RH after, measure IV curve equally.F.F. is derived respectively from each IV curve, the F.F. after leaving standstill under hot and humid atmosphere gas and value (the F.F.(Oh)-F.F.(1500h that obtains will be deducted in F.F. before leaving standstill under hot and humid atmosphere gas)) as Delta(F.F.), with it as average index.Usually, Delta(F.F.) if value be less than 0.2, be then judged as that connection reliability is good.
Known in embodiment 1 ~ 9 and reference example 1, the aligned in position of electrode/bond layer/distribution component (metal forming) is easy, and connection temperature is the temperature (170 DEG C) lower than the connection temperature of solder in the past, does not find the warpage of substrate.In addition, the syndeton of the embodiment 1 ~ 9 that the metal forming adhesive tape being the band bonding agent of 0.8 ~ 3 by the thickness t of bond layer and the ratio t/Ry of maximum height Ry in alligatoring face of metal forming that arranges this bond layer makes all shows fully little Delta(F.F.), excellent on connection reliability.And on the other hand, be that the syndeton of the reference example 1 that the metal forming adhesive tape of the band bonding agent of 4 makes has and is difficult to obtain initial stage conducting by t/Ry, deltaF.F. becomes large tendency.In addition, the syndeton of the comparative example 1 using smoothing electrolytic Copper Foil to obtain can not get initial stage conducting.
As described above, according to the present invention, a kind of like this metal forming adhesive tape with bonding agent can be provided, it not only can carry out the connection of electrode and distribution component in 1 operation, can realize being electrically connected solar battery cell each other time the simplification of connection operation, and, can connect at than temperature (particularly less than 200 DEG C) low during use solder, the fire damage to solar battery cell can be reduced.In addition, by using the metal forming adhesive tape of such band bonding agent, productivity ratio the solar module with high reliability can be manufactured better.
Industrial application
According to the present invention, a kind of connection operation that can not only simplify when being electrically connected each other by electric conductor disconnected from each other can be provided, and the conductor connection member of excellent connection reliability can be obtained.In addition, according to the present invention, a kind of syndeton and the solar module that can take into account excellent productivity and high connecting reliability can be provided.
Claims (109)
1. a conductor connection member, it possesses: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming,
Described bond layer contains epoxy resin and latent curing agent,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is less than 3 times of described Ry,
The unit of described Ry and t is micron.
2. a conductor connection member, it possesses: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming,
Described bond layer contains epoxy resin, latent curing agent and conducting particles,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the average grain diameter D of described conducting particles is described below Ry,
The unit of described Ry and D is micron.
3. a conductor connection member, it possesses: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming,
Described bond layer contains epoxy resin, latent curing agent and conducting particles,
10 mean roughness being formed with the described alligatoring face of described bond layer are set to Rza, when 10 mean roughness in the face connected with described bond layer of the electric conductor be connected are set to Rzb, the maximum particle diameter r of described conducting particles
maxbe less than or equal to described Rza and described Rzb sum,
Described Rza, Rzb and r
maxunit be micron.
4. a conductor connection member, it possesses: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming,
Described bond layer contains epoxy resin, latent curing agent and conducting particles,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the average grain diameter D of described conducting particles is described below Ry,
10 mean roughness being formed with the described alligatoring face of described bond layer are set to Rza, when 10 mean roughness in the face connected with described bond layer of the electric conductor be connected are set to Rzb, the maximum particle diameter r of described conducting particles
maxbe less than or equal to described Rza and described Rzb sum,
Described Ry, D, Rza, Rzb and r
maxunit be micron.
5. a conductor connection member, it possesses: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming,
Described bond layer contains epoxy resin and latent curing agent,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the average grain diameter Dc of described latent curing agent is described below Ry,
The unit of described Ry and Dc is micron.
6. conductor connection member according to claim 3, wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is less than 3 times of described Ry,
The unit of described Ry and t is micron.
7. the conductor connection member according to any one of claim 2,4 ~ 5, wherein, the thickness t of described bond layer is less than 3 times of described Ry,
The unit of described t is micron.
8. conductor connection member according to claim 3, wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 0.7 ~ 3 times of described Ry,
The unit of described Ry and t is micron.
9. the conductor connection member according to any one of claim 2,4 ~ 5, wherein, the thickness t of described bond layer is 0.7 ~ 3 times of described Ry,
The unit of described t is micron.
10. conductor connection member according to claim 3, wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 0.7 ~ 1.2 times of described Ry,
The unit of described Ry and t is micron.
11. conductor connection members according to any one of claim 2,4 ~ 5, wherein, the thickness t of described bond layer is 0.7 ~ 1.2 times of described Ry,
The unit of described t is micron.
12. conductor connection members according to claim 3, wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 1 ~ 2 times of described Ry,
The unit of described Ry and t is micron.
13. conductor connection members according to any one of claim 2,4 ~ 5, wherein, the thickness t of described bond layer is 1 ~ 2 times of described Ry,
The unit of described t is micron.
14. conductor connection members according to claim 3, wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 2 ~ 3 times of described Ry,
The unit of described Ry and t is micron.
15. conductor connection members according to any one of claim 2,4 ~ 5, wherein, the thickness t of described bond layer is 2 ~ 3 times of described Ry,
The unit of described t is micron.
16. conductor connection members according to any one of Claims 1 to 5, wherein, the thickness of described bond layer is 5 ~ 50 μm.
17. conductor connection members according to any one of Claims 1 to 5, wherein, the thickness of described bond layer is 9 ~ 45 μm.
18. conductor connection members according to any one of Claims 1 to 5, wherein, described epoxy resin is for being selected from by bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, Bisphenol F novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanuric acid ester type epoxy resin, at least one resin in the group of aliphat chain epoxy resin composition.
19. conductor connection members according to claim 1, wherein, described bond layer contains conducting particles.
20. conductor connection members according to claim 5, wherein, described bond layer contains conducting particles.
21. conductor connection members according to any one of Claims 1 to 5, wherein, described latent curing agent is anionic polymerization catalyst type curing agent, cationically polymerizable catalyst type curing agent or addition polymerization type curing agent.
22. conductor connection members according to any one of Claims 1 to 5, wherein, described latent curing agent is tertiary amines or imidazoles.
23. conductor connection members according to any one of Claims 1 to 5, wherein, described latent curing agent is aliphat sulfosalt.
24. conductor connection members according to any one of claim 2 ~ 4,19 ~ 20, wherein, described conducting particles is be selected from least one particle by gold particle, silver particles, copper particle, nickel particles, gold-plated nickel particle, gold-plated/nickel plastic pellet, copper facing particle, molecular group of nickel plating grain.
25. conductor connection members according to any one of claim 2 ~ 4,19 ~ 20, wherein, the domain size distribution of described conducting particles is in the scope of 1 ~ 50 μm.
26. conductor connection members according to any one of claim 2 ~ 4,19 ~ 20, wherein, the domain size distribution of described conducting particles is in the scope of 1 ~ 30 μm.
27. conductor connection members according to any one of claim 2 ~ 4,19 ~ 20, wherein, the content of described conducting particles is 10 below volume % using described bond layer cumulative volume as benchmark.
28. conductor connection members according to any one of claim 2 ~ 4,19 ~ 20, wherein, the content of described conducting particles take described bond layer cumulative volume as 0.1 ~ 7 volume % as benchmark.
29. conductor connection members according to any one of Claims 1 to 5, wherein, described metal forming is banded.
30. conductor connection members according to any one of Claims 1 to 5, wherein, described metal forming is the metal forming containing more than the a kind metal selected from Cu, Ag, Au, Fe, Ni, Pb, Zn, Co, Ti, Mg, Sn and Al.
31. conductor connection members according to any one of Claims 1 to 5, wherein, the maximum height Ry in described alligatoring face is 3 ~ 35 μm, and the unit of described Ry is micron.
32. conductor connection members according to any one of Claims 1 to 5, wherein, the maximum height Ry in described alligatoring face is 3 ~ 30 μm, and the unit of described Ry is micron.
33. conductor connection members according to any one of Claims 1 to 5, wherein, the maximum height Ry in described alligatoring face is 3 ~ 25 μm, and the unit of described Ry is micron.
34. conductor connection members according to any one of Claims 1 to 5, wherein, 10 mean roughness Rza in described alligatoring face are less than 30 μm, and the unit of described Rza is micron.
35. conductor connection members according to any one of Claims 1 to 5, wherein, 10 mean roughness Rza in described alligatoring face are less than 25 μm, and the unit of described Rza is micron.
36. conductor connection members according to any one of Claims 1 to 5, wherein, 10 mean roughness Rza in described alligatoring face are less than 15 μm, and the unit of described Rza is micron.
37. conductor connection members according to any one of Claims 1 to 5, it becomes metal forming in syndeton and solidfied material, and described syndeton possesses: the solar battery cell being formed with surface electrode; At least one face of interarea has alligatoring face and the metal forming configured in the mode that this alligatoring face is opposite with described surface electrode; With the solidfied material of the bond layer of the bonding described surface electrode of the mode being electrically connected described surface electrode and described metal forming and described metal forming.
38. 1 kinds of parts are for the application in being electrically connected each other by electric conductor, and wherein, described parts possess: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming,
Described bond layer contains epoxy resin and latent curing agent,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is less than 3 times of described Ry,
The unit of described Ry and t is micron.
39. 1 kinds of parts are for the application in being electrically connected each other by electric conductor, and wherein, described parts possess: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming,
Described bond layer contains epoxy resin, latent curing agent and conducting particles,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the average grain diameter D of described conducting particles is described below Ry,
The unit of described Ry and D is micron.
40. 1 kinds of parts are for the application in being electrically connected each other by electric conductor, and wherein, described parts possess: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming,
Described bond layer contains epoxy resin, latent curing agent and conducting particles,
10 mean roughness being formed with the described alligatoring face of described bond layer are set to Rza, when 10 mean roughness in the face connected with described bond layer of the electric conductor be connected are set to Rzb, the maximum particle diameter r of described conducting particles
maxbe less than or equal to described Rza and described Rzb sum,
Described Rza, Rzb and r
maxunit be micron.
41. 1 kinds of parts are for the application in being electrically connected each other by electric conductor, and wherein, described parts possess: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming,
Described bond layer contains epoxy resin, latent curing agent and conducting particles,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the average grain diameter D of described conducting particles is described below Ry,
10 mean roughness being formed with the described alligatoring face of described bond layer are set to Rza, when 10 mean roughness in the face connected with described bond layer of the electric conductor be connected are set to Rzb, the maximum particle diameter r of described conducting particles
maxbe less than or equal to described Rza and described Rzb sum,
Described Ry, D, Rza, Rzb and r
maxunit be micron.
42. 1 kinds of parts are for the application in being electrically connected each other by electric conductor, and wherein, described parts possess: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming,
Described bond layer contains epoxy resin and latent curing agent,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the average grain diameter Dc of described latent curing agent is described below Ry,
The unit of described Ry and Dc is micron.
43. application according to claim 40, wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is less than 3 times of described Ry,
The unit of described Ry and t is micron.
44. application according to any one of claim 39,41 ~ 42, wherein, the thickness t of described bond layer is less than 3 times of described Ry,
The unit of described t is micron.
45. application according to claim 40, wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 0.7 ~ 3 times of described Ry,
The unit of described Ry and t is micron.
46. application according to any one of claim 39,41 ~ 42, wherein, the thickness t of described bond layer is 0.7 ~ 3 times of described Ry,
The unit of described t is micron.
47. application according to claim 40, wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 0.7 ~ 1.2 times of described Ry,
The unit of described Ry and t is micron.
48. application according to any one of claim 39,41 ~ 42, wherein, the thickness t of described bond layer is 0.7 ~ 1.2 times of described Ry,
The unit of described t is micron.
49. application according to claim 40, wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 1 ~ 2 times of described Ry,
The unit of described Ry and t is micron.
50. application according to any one of claim 39,41 ~ 42, wherein, the thickness t of described bond layer is 1 ~ 2 times of described Ry,
The unit of described t is micron.
51. application according to claim 40, wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 2 ~ 3 times of described Ry,
The unit of described Ry and t is micron.
52. application according to any one of claim 39,41 ~ 42, wherein, the thickness t of described bond layer is 2 ~ 3 times of described Ry,
The unit of described t is micron.
53. application according to any one of claim 38 ~ 42, wherein, the thickness of described bond layer is 5 ~ 50 μm.
54. application according to any one of claim 38 ~ 42, wherein, the thickness of described bond layer is 9 ~ 45 μm.
55. application according to any one of claim 38 ~ 42, wherein, described epoxy resin is for being selected from by bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, Bisphenol F novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanuric acid ester type epoxy resin, at least one resin in the group of aliphat chain epoxy resin composition.
56. according to application according to claim 38, and wherein, described bond layer contains conducting particles.
57. application according to claim 42, wherein, described bond layer contains conducting particles.
58. application according to any one of claim 38 ~ 42, wherein, described latent curing agent is anionic polymerization catalyst type curing agent, cationically polymerizable catalyst type curing agent or addition polymerization type curing agent.
59. application according to any one of claim 38 ~ 42, wherein, described latent curing agent is tertiary amines or imidazoles.
60. application according to any one of claim 38 ~ 42, wherein, described latent curing agent is aliphat sulfosalt.
61. application according to any one of claim 39 ~ 41,56 ~ 57, wherein, described conducting particles is be selected from least one particle by gold particle, silver particles, copper particle, nickel particles, gold-plated nickel particle, gold-plated/nickel plastic pellet, copper facing particle, molecular group of nickel plating grain.
62. application according to any one of claim 39 ~ 41,56 ~ 57, wherein, the domain size distribution of described conducting particles is in the scope of 1 ~ 50 μm.
63. application according to any one of claim 39 ~ 41,56 ~ 57, wherein, the domain size distribution of described conducting particles is in the scope of 1 ~ 30 μm.
64. application according to any one of claim 39 ~ 41,56 ~ 57, wherein, the content of described conducting particles is 10 below volume % using described bond layer cumulative volume as benchmark.
65. application according to any one of claim 39 ~ 41,56 ~ 57, wherein, the content of described conducting particles take described bond layer cumulative volume as 0.1 ~ 7 volume % as benchmark.
66. application according to any one of claim 38 ~ 42, wherein, described metal forming is banded.
67. the application according to any one of claim 38 ~ 42, wherein, described metal forming is the metal forming containing more than the a kind metal selected from Cu, Ag, Au, Fe, Ni, Pb, Zn, Co, Ti, Mg, Sn and Al.
68. application according to any one of claim 38 ~ 42, wherein, the maximum height Ry in described alligatoring face is 3 ~ 35 μm, and the unit of described Ry is micron.
69. application according to any one of claim 38 ~ 42, wherein, the maximum height Ry in described alligatoring face is 3 ~ 30 μm, and the unit of described Ry is micron.
70. application according to any one of claim 38 ~ 42, wherein, the maximum height Ry in described alligatoring face is 3 ~ 25 μm, and the unit of described Ry is micron.
71. application according to any one of claim 38 ~ 42, wherein, 10 mean roughness Rza in described alligatoring face are less than 30 μm, and the unit of described Rza is micron.
72. application according to any one of claim 38 ~ 42, wherein, 10 mean roughness Rza in described alligatoring face are less than 25 μm, and the unit of described Rza is micron.
73. application according to any one of claim 38 ~ 42, wherein, 10 mean roughness Rza in described alligatoring face are less than 15 μm, and the unit of described Rza is micron.
74. 1 kinds of parts are in the application for being carried out each other by electric conductor in the manufacture of the conductor connection member be electrically connected, wherein, described parts possess: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming
Described bond layer contains epoxy resin and latent curing agent,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is less than 3 times of described Ry, and the unit of described Ry and t is micron.
75. 1 kinds of parts are in the application for being carried out each other by electric conductor in the manufacture of the conductor connection member be electrically connected, wherein, described parts possess: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming
Described bond layer contains epoxy resin, latent curing agent and conducting particles,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the average grain diameter D of described conducting particles is described below Ry,
The unit of described Ry and D is micron.
76. 1 kinds of parts are in the application for being carried out each other by electric conductor in the manufacture of the conductor connection member be electrically connected, wherein, described parts possess: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming
Described bond layer contains epoxy resin, latent curing agent and conducting particles,
10 mean roughness being formed with the described alligatoring face of described bond layer are set to Rza, when 10 mean roughness in the face connected with described bond layer of the electric conductor be connected are set to Rzb, the maximum particle diameter r of described conducting particles
mabe less than or equal to described Rza and described Rzb sum,
Described Rza, Rzb and r
maxunit be micron.
77. 1 kinds of parts are in the application for being carried out each other by electric conductor in the manufacture of the conductor connection member be electrically connected, wherein, described parts possess: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming
Described bond layer contains epoxy resin, latent curing agent and conducting particles,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the average grain diameter D of described conducting particles is described below Ry,
10 mean roughness being formed with the described alligatoring face of described bond layer are set to Rza, when 10 mean roughness in the face connected with described bond layer of the electric conductor be connected are set to Rzb, the maximum particle diameter r of described conducting particles
mabe less than or equal to described Rza and described Rzb sum,
Described Ry, D, Rza, Rzb and r
maxunit be micron.
78. 1 kinds of parts are in the application for being carried out each other by electric conductor in the manufacture of the conductor connection member be electrically connected, wherein, described parts possess: the metal forming at least one face of interarea with alligatoring face and the bond layer formed on the described alligatoring face of this metal forming
Described bond layer contains epoxy resin and latent curing agent,
When the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the average grain diameter Dc of described latent curing agent is described below Ry,
The unit of described Ry and Dc is micron.
79. according to the application described in claim 76, and wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is less than 3 times of described Ry, and the unit of described Ry and t is micron.
80. application according to any one of claim 75,77 ~ 78, wherein, the thickness t of described bond layer is less than 3 times of described Ry, and the unit of described t is micron.
81. according to the application described in claim 76, and wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 0.7 ~ 3 times of described Ry, and the unit of described Ry and t is micron.
82. application according to any one of claim 75,77 ~ 78, wherein, the thickness t of described bond layer is 0.7 ~ 3 times of described Ry, and the unit of described t is micron.
83. according to the application described in claim 76, and wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 0.7 ~ 1.2 times of described Ry, and the unit of described Ry and t is micron.
84. application according to any one of claim 75,77 ~ 78, wherein, the thickness t of described bond layer is 0.7 ~ 1.2 times of described Ry, and the unit of described t is micron.
85. according to the application described in claim 76, and wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 1 ~ 2 times of described Ry, and the unit of described Ry and t is micron.
86. application according to any one of claim 75,77 ~ 78, wherein, the thickness t of described bond layer is 1 ~ 2 times of described Ry, and the unit of described t is micron.
87. according to the application described in claim 76, and wherein, when the maximum height in the described alligatoring face being formed with described bond layer is set to Ry, the thickness t of described bond layer is 2 ~ 3 times of described Ry, and the unit of described Ry and t is micron.
88. application according to any one of claim 75,77 ~ 78, wherein, the thickness t of described bond layer is 2 ~ 3 times of described Ry, and the unit of described t is micron.
89. application according to any one of claim 74 ~ 78, wherein, the thickness of described bond layer is 5 ~ 50 μm.
90. application according to any one of claim 74 ~ 78, wherein, the thickness of described bond layer is 9 ~ 45 μm.
91. application according to any one of claim 74 ~ 78, wherein, described epoxy resin is for being selected from by bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, Bisphenol F novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanuric acid ester type epoxy resin, at least one resin in the group of aliphat chain epoxy resin composition.
92. according to the application described in claim 74, and wherein, described bond layer contains conducting particles.
93. according to the application described in claim 78, and wherein, described bond layer contains conducting particles.
94. application according to any one of claim 74 ~ 78, wherein, described latent curing agent is anionic polymerization catalyst type curing agent, cationically polymerizable catalyst type curing agent or addition polymerization type curing agent.
95. application according to any one of claim 74 ~ 78, wherein, described latent curing agent is tertiary amines or imidazoles.
96. application according to any one of claim 74 ~ 78, wherein, described latent curing agent is aliphat sulfosalt.
97. application according to any one of claim 75 ~ 77,92 ~ 93, wherein, described conducting particles is be selected from least one particle by gold particle, silver particles, copper particle, nickel particles, gold-plated nickel particle, gold-plated/nickel plastic pellet, copper facing particle, molecular group of nickel plating grain.
98. application according to any one of claim 75 ~ 77,92 ~ 93, wherein, the domain size distribution of described conducting particles is in the scope of 1 ~ 50 μm.
99. application according to any one of claim 75 ~ 77,92 ~ 93, wherein, the domain size distribution of described conducting particles is in the scope of 1 ~ 30 μm.
100. application according to any one of claim 75 ~ 77,92 ~ 93, wherein, the content of described conducting particles is 10 below volume % using described bond layer cumulative volume as benchmark.
101. application according to any one of claim 75 ~ 77,92 ~ 93, wherein, the content of described conducting particles take described bond layer cumulative volume as 0.1 ~ 7 volume % as benchmark.
102. application according to any one of claim 74 ~ 78, wherein, described metal forming is banded.
103. the application according to any one of claim 74 ~ 78, wherein, described metal forming is the metal forming containing more than the a kind metal selected from Cu, Ag, Au, Fe, Ni, Pb, Zn, Co, Ti, Mg, Sn and Al.
104. application according to any one of claim 74 ~ 78, wherein, the maximum height Ry in described alligatoring face is 3 ~ 35 μm.
105. application according to any one of claim 74 ~ 78, wherein, the maximum height Ry in described alligatoring face is 3 ~ 30 μm.
106. application according to any one of claim 74 ~ 78, wherein, the maximum height Ry in described alligatoring face is 3 ~ 25 μm.
107. application according to any one of claim 74 ~ 78, wherein, 10 mean roughness Rza in described alligatoring face are less than 30 μm.
108. application according to any one of claim 74 ~ 78, wherein, 10 mean roughness Rza in described alligatoring face are less than 25 μm.
109. application according to any one of claim 74 ~ 78, wherein, 10 mean roughness Rza in described alligatoring face are less than 15 μm.
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| JP2007124439 | 2007-05-09 | ||
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| JP2007-228035 | 2007-09-03 | ||
| CN2008800148266A CN101675484B (en) | 2007-05-09 | 2008-05-07 | Conductor connection member, connection structure, and solar cell module |
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| CN2008800148266A Division CN101675484B (en) | 2007-05-09 | 2008-05-07 | Conductor connection member, connection structure, and solar cell module |
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| CN2008800148266A Ceased CN101675484B (en) | 2007-05-09 | 2008-05-07 | Conductor connection member, connection structure, and solar cell module |
| CN201110112703XA Pending CN102270669A (en) | 2007-05-09 | 2008-05-07 | Conductor connection member, connection structure, and solar cell module |
| CN2011102050656A Pending CN102332478A (en) | 2007-05-09 | 2008-05-07 | Conductor connection member, connection structure, and solar cell module |
| CN201210211275.0A Active CN102723381B (en) | 2007-05-09 | 2008-05-07 | Conductor connection member |
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| CN2008800148266A Ceased CN101675484B (en) | 2007-05-09 | 2008-05-07 | Conductor connection member, connection structure, and solar cell module |
| CN201110112703XA Pending CN102270669A (en) | 2007-05-09 | 2008-05-07 | Conductor connection member, connection structure, and solar cell module |
| CN2011102050656A Pending CN102332478A (en) | 2007-05-09 | 2008-05-07 | Conductor connection member, connection structure, and solar cell module |
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Also Published As
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|---|---|
| CN103545402B (en) | 2018-09-25 |
| TWI547539B (en) | 2016-09-01 |
| KR20120029485A (en) | 2012-03-26 |
| KR101157771B1 (en) | 2012-06-25 |
| CN101675484B (en) | 2012-07-04 |
| CN102332478A (en) | 2012-01-25 |
| CN103545402A (en) | 2014-01-29 |
| EP2146355A1 (en) | 2010-01-20 |
| TW201641646A (en) | 2016-12-01 |
| TW201213495A (en) | 2012-04-01 |
| KR101101464B1 (en) | 2012-01-03 |
| JPWO2008139994A1 (en) | 2010-08-05 |
| US20100116314A1 (en) | 2010-05-13 |
| US10186627B2 (en) | 2019-01-22 |
| JP2012186486A (en) | 2012-09-27 |
| CN102270669A (en) | 2011-12-07 |
| KR20110082199A (en) | 2011-07-18 |
| CN102723381A (en) | 2012-10-10 |
| US20150200324A1 (en) | 2015-07-16 |
| TW201514275A (en) | 2015-04-16 |
| TWI602899B (en) | 2017-10-21 |
| TWI520159B (en) | 2016-02-01 |
| TWI655266B (en) | 2019-04-01 |
| TW200912964A (en) | 2009-03-16 |
| CN101675484A (en) | 2010-03-17 |
| TW201802209A (en) | 2018-01-16 |
| JP5115553B2 (en) | 2013-01-09 |
| TWI486423B (en) | 2015-06-01 |
| KR20090106395A (en) | 2009-10-08 |
| WO2008139994A1 (en) | 2008-11-20 |
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